Anthraquinone dyestuffs

ABSTRACT

DYESTUFFS OF THE FORMULAE   1-(R-NH-),4-(Y-NH-),DI((Z)(0-2)-)ANTHRAQUINONE (I)   1-(R-NH-),4-Y1,5,8-DI(X-),DI((Z)(0-2)-)ANTHRAQUINONE (II)   AND 1,4-DI(R-NH-),DI((Z)(O-2)-)ANTHRAQUINONE (III)   WHEREIN Z IS A SUBSTITUENT, ONE X IS A MEMBER NHR AND THE OTHER IS HYDROGEN OR A SUBSTITUTED Z, Y IS AN OPTIONALLY SUBSTITUTED HYDROCARBON RESIDUE OR AN ACYL GROUP, Y1 IS HYDROGEN OR A SUBSTITUENT, AND R IS A MOIETY   CO-B-CO-NH-E   WHERE B IS A BOND, SATURATED OR UNSATURATED ALKYLENE WITH OR WITHOUT HETERO ATOMS AND SUBSTITUENTS, MONO OR POLYNUCLEAR ARYLENE WITH OR WITHOUT SUBSTITUENTS, CYCLOALKYLENE WITH OR WITHOUT SUBSTITUENTS OR HETEROARYLENE WITH OR WITHOUT SUBSTITUENTS AND E IS A RADICAL B OR AN ARALKYL GROUP; AS WELL AS THEIR PREPARATION AND USE AS PIGMENTS THE NOVEL DYESTUFFS ARE PIGMENT DYESTUFFS AND FREE OF SULFONIC ACID AND CARBOXYLIC ACID GROUPS.

United States Patent Oflice 3,699,126 Patented Oct. 17, 1972 US. Cl.260329.2 2 Claims ABSTRACT OF THE DISCLOSURE Dyestuffs of the formulaeand ll NHR (III) wherein Z is a substituent, one X is a member NHR andthe other is hydrogen or a substituent Z, Y is an optionally substitutedhydrocarbon residue or an acyl group, Y, is hydrogen or a substituent,and R is a moiety where B is a bond, saturated or unsaturated alkylenewith or without hetero=atoms and substituents, mono or polynucleararylene with or without substituents, cycloalkylene with or withoutsubstituents or heteroarylene with or without substituents and E is aradical B or an aralkyl group; as well as their preparation and use aspigments'the novel dyestuffs are pigment dyestuffs and free of sulfonicacid and carboxylic acid groups. v y

DISCLOSURE so The subject matter of the present invention comprisesdyestuffs of the formula XI I (Z)0-2 C I [\lj-(ZM-a in wherein Z is asubstituent preferably selected from the group comprising hydrogen;halogen such as chlorine, fluorine or bromine; alkyl, preferably Calkyl; nitro; amino; hydroxy; cyano; carboxy; alkoxy, preferablycontaining 1 to 3 carbon atoms; aryloxy, preferably phenyloxy, C alkylmercapto, aryl mercapto such as phenyl mercapto; aryl, especially phenylor naphthyl; C alkyl carbonyl amino such as acetyl amino, valeryl aminoand stearoyl amino; aryl carbonyl amino such as naphthoyl and benzoylamino; aryl sulfonyl amino, such as benzene sulfamide and C alkylsulfonyl amino; carbamoyl; aryl sulfonyl such as phenyl sulfonyl; Calkyl sulfonyl; carboxy alkyl esters wherein the alkyl members contain 1to 5 carbon atoms; carboxy aryl esters especially phenyl esters;s-ulfonic acid aryl esters, such as sulfonic acid phenyl esters;sulfonic acid alkyl esters with 1-6 carbon atoms; carbalkoxy with 1-5carbon atoms; carbaryloxy especially naphthyl or phenyl carbonyl;arylamino especially anilino; alkylamino with 1 to 17 carbon atoms;akenylamino with l to 17 carbon atoms; cycloalkylamino, preferablycyclohexyl amino; aralkylamino especially benzyl or phenyl ethyl amino;wherein the above mentioned cyclic radicals can contain 0 to 4substituents per ring selected from the group consisting of chlorine,fluorine, bromine, nitro, hydroxy, alkoxy, with 1 to 6 carbons,trihaloalkyl with 1-6 carbon atoms such as trifluoromethyl; alkylcarbonylamino with 1-6 carbon atoms such as acetyl amino, alkylcontaining 1 to 6 carbon atoms, sulfamoyl and cyano; X stands for amember Z or NHR wherein when one X is NHR, the others are Z; R standsfor the grouping COB-CO-NHE wherein B is selected from the groupconsisting of a single bond; saturated alkylene with 1 to 17 carbonatoms which can contain in the alkylene chain hetero atoms selected fromthe group consisting of O, S and NH and further including the members iO HN-R substituted alkylene and hetero-substtiuted alkylene chainswherein the substituents may be selected from the group consisting ofhydroxy, alkyl carbonyl amino with 1-6 carbons such as acetyl aminoalkoxy with 1-6 carbon atoms and carboxy; unsaturated alkylene with 1 to17 carbon atoms which may contain the same hetero atoms and substituentsmentioned for the saturated alkylene chain; mononuclear arylenepreferably phenylene; poly-nuclear arylenes such as naphthylene,byphenylene, azo benzene, azoxybenzene, hydrazobenzene, benzophenone,azo biphenyl, diphenyl methane, diphenyl ether, terphenyl, biphenyl azobiphenyl; cycloalkylene such as cycloheXyl, cyclopentyl andbicycloheptene; hetero arylene containing 5 or 6 members which maycontain hetero members selected from the group consisting of oxygen,sulfur, and nitrogen, especially furanyl, thiophenyl and pyridinylwherein the above cyclic members can contain 0-4 substituents per ring,selected from the group consisting of halogen-such as chlorine, fluorineand bromine, alkyl with Stilla noth er perchedsms -is 1-6 carbonatoms,'hydroxy, alkoxy with 1 to 6 carbon atoms, alkyl carbonylamino,such as acetyfamino, 'nit'ro;

The member E is selected from the group consisting of saturated alkylwith 1 to 18 carbon atoms which may contain hetero atoms" selected fromthe group consisting of O, S and NH further including the memberssubstituted saturated C alkyl with or without hetero atoms withsubstituents selected from the group consisting of hydroxy, alkoxy withl to 6 carbon atoms, carboxy,

and alkyl carbonyl amino with 1-6 carbons such as acetyl amino;unsaturated alkyl with 1 to 18 carbon atoms which may contain heteroatoms and/or substituents as defined-for the saturated alkyl members;cyclo alkyl with up to 9'carbon atoms, especially cyclohexyl andcycloalkyl which may further contain 1 or more hetero atoms seectedfrom'the group consisting of nitrogen, oxygen,-an'd sulfur, especiallysulfur cyclopentyl S,S dioxide; aralkyl,

preferably benzyl but including phenyl ethyl and includingheXahydrobenzyl; mono or polycycloarylsuch' as yl,triazolyl,'benzotriazolyl, thiazolyl, benzothiazolyl, pi-

perazinyl, furanyl and thiophenyl; or cycloalkylene sulfones, with up to9 members per ring; where the cyclic members listed above can contain -4substituents 'per ring selected from the group consisting ofhalogen suchas chlorine, bromine, fluorine, nitro, alkyl with 1 i012 carbon atoms,hydroxy alkyl with 1 to 12 carbon atoms, cyclo alkyl such as cyclohexyl,trihalo alkyl such as trifiuoromethyl, hydroxy, alkoxy with 1 to3-carbon atoms, aryloxy such as phenoxy, carboxy, alkyl carbonylaminosuch as acetylamino, cyano, arylamino especially phenylamino which maycontain further substituents suchas methyl and methoxy, alkyl sulfonylwith'l to '6 carbon atoms, aryl sulfonyl such as phenyl sulfonyl,alkycarbonyl with 1 to 6 carbon atoms, aryl carbonyl such as phenylcarbonyl, canboxy alkyl esters with'l to- 6 carbon atoms, sulfamoyl,which can contain as N sub'stituents tolyl, hydroxy alkylwith 1 to 6carbons such as hydroxy ethyl or phenyl radicals; alkyl or aryl sulfonylamino especially phenyl or methyl sulfonyl amino; carbonamide, phenylazo of phenyl azoxy which may contain carbonamide substituents. v I IOne preferred class of dyestuffs of Formulal is in whichY denotes Calkyl carbonyl, aryl carbonyl,

alkenyl, cycloalkyl, aralkyl wherein the aryl radicals can contain 0-4substituents per ring Selected from the group consisting 'of Cl, F, Br,N0 OH, (3P COCH CN,

,SOgNHg, alkyl with 1 to 6 carbon atoms and the alkoxy with l to 6carbon atoms.

Another preferred class is The 'icornpounds according t o',thi sinventi'o are prepared c sl 'si n n P epare ffqr m s; by acylating.antliraquinone derivatives of the formula U in which one of the X fscanbe an amino and the others are selected from the definitions given abovefor X and Z is as defined above.,These' compounds (II) are reacted withreactive derivatives': preferably the halides, anhydrides or alkylesters of dicarboxylic acid of the general formula COOH--B COOH in whichB is defined as above with at leastpne mole of the said reactivederivatives being used for every free amino group in (II) and bysubsequent reaction with an amine of the general formula NH E in whi'chE is as defined above by using at least one mole of the amine. for everygroup N H of (II) which is to be converted intoa radical NHR. Since thefirst preferred group of dyestuffs of "this invention are thosecontaining two radicals NHR the preparation according to this firstprocess involves two moles of acid and two moles of amine for each moleof anthraquinone (II) utilized.- In another preferred process a singleNHR radical is desired, thereby requiring only one mole of acid andamine.

The compounds canalso be prepared by known methods involving theacylatiorl of g'anthraquinone derivatives of the Formula II with atleast one'r nole per free NH group of a reactive deriyative of anN-substituted dicarboxylic acid monoamide of the formula I such, aspyridin Piperidine, morpholine, trimethylam'ine,

collidine,-picoline, alutidine, 'quinoline, with or without the additionof acid binding agents such as sodium carbonate, potassiumcarbonate,sodium or potassium bicarbonate or quick lime until the starting amineis completely converted and subsequently reacting the resulting compoundof the formula t Wliich B is'as defined above, and one of t headditional substituent X can be a radical NH"CO B-CO-j-A with the othersbeing as defined above for X after separation from the reaction solutionor without isolation with an excess of an amine of the formula NH E attemperatures between 40 and 220 C. with the use of the amine as solventor the use of an organic solvent such as benzene, toluene, xylene,chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene,optionally in the presence of basic catalysts such as pyridine,piperidine, morpholine, trimethylamine, collidine, picoline, lutidine,quinoline, with or without the addition of acid binding agents such assodium carbonate, potassium carbonate, sodium or potassium bicarbonateor quick lime.

Examples of amino anthraquinones (II) preferably used for thepreparation of the compounds (I) according to the invention are:

4-amino-1-methylamino anthraquinone, 4-amino-l-hexahydroanilinoanthraquinone, 4-amino-l-acetylamino anthraquinone,4-amino-l-chloroacetylarnino anthraquinone, 4-amino-1-butylam'inoanthraquinone, A-amino-l-stearoylamino anthraquinone,4-amino-1-benzoylamino anthraquinone, 4-amino-1- (2,3- or4-chlor0benzoylamino)-anthraquinone, 4-amino-1-(2,4- or2,5-dichlorobenzoylamino)-anthraquinone, 4-amino-1-(2,'3- or4-nitrobenzoylamino)-anthraquinone,4-amino-1-(4-chloro-3-nitrobenzoylamino)- anthraquinone,4-amino-1-(3,5-dinitrobenzoylamino)-anthraquinone, 4-amino-1-(3- or4-trifluoromethylbenzoylamino)- anthraquinone,4-amino-l-(4-methylbenzoylamino)-anthraquinone, 4-amino- 1-(4-methoxybenzoylamino -anthraquinone,4-amino-1-(3=sulfamoylbenzoylamino )-anthraquinone, 4-amino-3-methyl- 1-(4-chlorobenzoylamino anthraquinone, I4-amino-5-nitro-1-benzoylamino-anthraquinone, 4-amino-3-bromo- 1- (paratoluenesulfamido anthraquinone, 4-amino-l-anilino anthraquinone,4-amino-1- (4-methoxyanilino)-anthraquinone,4-amino-3-bromo-1-(4-methylanilino)-anthraquinone, 4-amino-3-bromo- 1-(2,6-diethyl-4-methylanilino anthraquinone, 4-amino-1-( 2- 1 or.4-bromobenzoylamino)-anthraquinone, 1,4-diamino-anthraquinone, Z-bromo-1,4-diamino-anthra quinone, 2,3-dichloro-1,4-diaminoanthraquinone,5,8-dichloro-1, 4-diaminoanthraquinone,2-nitro-1,4-diamino-anthraquinone, S-nitro-1,4-diamino-anthraquinone,2-bromo-5-nitro-1,4-diamino-anthraquinone,S-benzoyl-amino-l,4-diamino-anthraquinone,S-actylamino-1,4-diamino-anthraquinone,1,4-diamino-5,8-dihydroxy-anthraquinone,1,4-diamino-2-phenoxy-anthraquinone, I1,4-diarnino-2,3-diphenoxy-anthraquinone, 1,4-diamino-5,8-dihydroxy-2phenylmercapto anthraquinone,6-brorno-1,4-diamino-5,8-dihydroxy-2-phenylmercaptoanthraquinone,1,4-diamino-2-phenylsulphonyl-anthraquinone, -nitro-1,4-diamino-2-(4-chloro-phenylsulphonyl)- anthraquinone,1,4-diamino-anthraquinone-2-sulphonic acid-phenyl ester,1,4-diamino-2-(4-methoxy-phenyl)-3-cyanoanthraquinone,1,4-diamino-anthraquinone-B-carboxylic acid amide, ethyl ester and butylester.

Further examples of amino-anthraquinones of the Formula II preferablyused for the preparation ofvthe compounds according to the inventionare:

bromine atom per mol of 4,8-diamino-1,5-dihydroxyor4,5-diamino-1,S-diIiydroxy-anthraquinone; 3-bromo-l,

4,8-triamino-5-hydroxy-anthraquinone, 2-bromo-4,5,8-triamino 1hydroxy-anthraquinone or 2-(4-methoxyphenyl) -1,5-diamino-4,8-dihydroxy-anthraquinone.

The reactive derivatives of the dicarboxylic acids preferably includethe halides especially the fluorides, chlorides, and bromides as well asthe esters and anhydr'ides, particularly the alkyl esters and especiallythe methyl or ethyl esters. Aliphatic dicarboxylic acids may be used'such as oxalic, malonic, succinic, glutaric, adipic, suberic, azelaic,sebacic; aliphatic dicarboxylic acids containing hereto atoms such asdiglycolic acid, thio diglycolic acid,

methylene-bis-thioglycolic acid, di-thio-diglycolic acid,

imino-diacetic acid; substituted aliphatic dicarboxylic acids such as,heptadecane-dicarboxylic acid-(1,8) or 1,9), hydroxy-succinic acid,acetone-dicarboxylic acid, acetylamino-succinic acid, Z-acetyIaminogIutaric acid; cycloaliphatic dicarboxylic acids, such ascyclohexanedicar-boxylic acid-(1,2) or -(1,4), cam-pheric acid; bicyclicdicarboxylic acids, such as bicyclo[2,2,1]-heptene- (5)-dicarboxylicacid(2,3); unsaturated dicarboxylic acids; such as fumaric acid,1,2,3,G-tetrahydro-phthalic acid; mononuclear arylene-dicarboxylicacids, such as benzene dicarboxylic acid-(1,2), -(1,3) or -(1,4), 4chloro isophthalic acid, 5 nitro isophthalic acid, 2-chloro-terephthalicacid, 2-nitro-terephthalic acid, '2,5-

dichloro-terephthalic acid, 4-hydroxy-isophthalic acid,2,5-dimethoxy-terephthalic acid, 2,5-difluoro-terephthalic acid,tetrachloro or tetrafluoro-terephthalic acid; poly-- nuclear condensedarylene-dicarboxylic acids, such as naphthalene-dicarboxylic acid-(1,4),-(1,5) or -(2,6); polynuclear annellated arylene-dicarboxylic acids,such as diphenyl-dicarboxylic acid (4,4'), diphenyl-sulphonedicarboxylicacid-(4,4'), azobenzene-dicarboxylic acid- (4,4'),azoxybenzene-dicarboxylic acid-(4,4), hydrazobenzene-dicarboxylicacid-(4,4'), henzophenone-dicarboxylic acid-(2,4),diphenylether-dicarboxylic acid-(4,4');

diphenylmethane dicanboxylic acid(4,4), p-terphenyldicarboxylicacid-(4,4'), 4 -carboxy-biphenyl-4-azo-4 biphenyl-carboxylic' acids-(4),or hetero-arylene-dicar boxylic acids such as 2,5-furan-dicarboxylicacid, 2,5- thiophene-dicarboxylic acid, pyridine-dicarboxylic acid- )7or I Examples of amines of the formula NH Eserving for the preparationof the compounds used according to the invention are:

Aliphatic amines such as methylamine, ethylamin'e, propylamine, n-,isoand tert.-butylamine, dodecyl-, tetradecylor 'hexadec'ylamine,9-amino-heptadecane, stearylamine; substituted aliphatic amines, such asZ-a'minoor l-amino-ethanol, 3-amino-propanol, amino-acetic acid,

6-amino-hexanic acid; amino-alkanes with chain-posh tioned hetero atom,such as 2-(2-amino-ethyl-amino)- ethanol-(1), 3 methoxy propylamine,3-ethoxy-propylamine, 3-butyloxy-propylamine, 3-(2-ethyl-hexyloxy)'-propylamine, Z-amino-diethyl sulphide; alkenyl-amines, such asallylamine; cycloalkyl-amines, .such as cyclohexylamine,2-(2-hydroxy-ethyl)-cyclohexylamine, 2-, 3- or 74-methyl-cyclohexylamine, hexahydro -benzylamine; cycloalkyl-amines withinterrupting hetero atoms in the alkylene chain, such asB-amino-sulpholane, N-(Z-aminoethyl)-piperazine; aral kyl-amines, suchas benzylamine, l-amino-lor -2-phenyl-ethane, w-amino-acetophenone;optionally substituted aryl-amines with optionally anneallated orcondensed arylnuclei, such as aniline, 2-, 3- or 4-chloro-aniline, 2,3-,2,4-, 2,5-, 3,4- or 3,5-dichloroaniline, 2,4,5-trichloroani1ine, 2-, 3-or 4-nitroaniline, 4-chloro-2-nitro-aniline, 5-chloro-2-nitro-aniline,3-chloro- 4-nitro-aniline, 2,5- dichloro-4-nitro-aniline,2,4-dinitroaniline, 6-bromo-2,4-dinitro-aniline, 2-, 3- or4-aminotoluene, 2-, 3- or 4-amino-benzotri fluoride, 4-chloro-2-amino-toluene, 5-chloro-2-aminobenzotrifluoride,4,5-dichloro-Z-amino-toluene, 4-, 5- or 6-nitro-2-amino-toluene,4-chIoro-3-amino-toluene or -benzotrifiuoride, 2-ethylaniline,xylidines, S-amino 1,3 bis-triiluoromethyl-benzene,2-amino-1,3,5-trimethyl-benzene, 4-amino-l-methy1- 3,5-diethy1-benzene,4-amino 1,3 dimethyl-S-ethylbenzene, 4 dodecyl aniline, 5,6,7,8tetrahydro naphthylamine-(1), or -(2), 4-amino-l-cyclohexylbenzene, 1-or 2 amino naphthalene, 2 amino anthracene, l-aminopyrene,6-amino-chrysene, 2- or 4-amino-diphenylamine, 4-amino-4'-methyldiphenylamine, 3-amino-4-methyl-diphenylamine, 2-, 3- or4-amino-diphenyl ether, 2-, 3- or 4-amino-l-methoxy-benzene,4-chloro-5-nitro-2-amino-lmethoxy-benzene, 4'-amin'o 4methoxy-diphenylamine, Z-hydroxyethyl (4-amino-phenyl -sulphone,methyl-(4- amino-phenyl)-sulphone, 4-amino 3 methoxy-diphenylamine, 4amino -l,3 dimethoxy benzene, 6-chloro-4- amino-1,3-dimethoxy-benzene,2-amino-l,4-diethoxy-benzone, 3-amino 4 methoxy-diphenylsulphone,4-aminoacetophenone, 4-amino-benzophenone, 2-, 3- or 4-aminobenzamide,4-amino-benzoic acid-methyl or -ethyl ester, 3-nitro-4-amino-benzamide,4-chloro 2 amino-benzonitrile, 4-amino-isophthalic acid dinitrile,A-amino-isophthalic acid diamide, G-amino-naphthoic acid amide-(2),

3-, or 4-amino-benzene-sulphonic acid amide, 3-aminobenzene-sulphonicacid-(2-hydroxyethyl)-amide, 4-aminobenzene-sulphonic, acid anilide,2-amino-benzoic acidsulphonic acid (4) diamide, 4 amino azobenzene, 4amino azobenzene carbonamide-(4'); or heteroaromatic aminessuch as 3- or2-aminodibenzofuran, 2 amino pyridine, 2 aminometh'yl pyridine, 9-ethy1-3 amino carbazole, 2 amino 4 methylpyrimidine, 3-amino 1,2,4 triazole,S-amino-Z-phenyl-benzotriazole, 2-amino thiazole, 2 amino benzothiazole,6-amino-2- methyl-benzothiazole, or 6-methoxy 2 lamino-benzothiazo-le'.I

The dyestuffs so prepared are obtained in a form suitable for pigments,or they can be brought into a fine division by a knownafter-treatment,-in order to be converted into a form suitable forpigments, for example, by dissolving or swelling them in stronginorganic acids such as sulphuric acid and pouring the mixture on toice. The fine division can also be achieved by grinding with or withoutgrinding auxiliaries, such as inorganic salts or sand, optionally in thepresence of solvents such as toluene, xylene, dichlorobenzene orN-methyl-pyrrolidone. The strength of colour and the transparency of thepigments can be influenced by varying the after-treatment..

The pigments used according .to the invention can be used for theproduction of very fast pigmented systems, such as mixtures with othersubstances, preparations, coating agents, printing colours, colouredpaper and coloured macromolecular materials. The term mixture with othersubstances comprises, for example, mixtures with inorganic whitepigments such as titanium dioxide (rutile) or with cement. Preparationsare, for example, flush pastes with organic liquids, or pastes and finepastes with Water, dispersing agents and possibly preservatives. Theterm coating agent stands, for example, for physically or oxidativelydrying lacquers, stoving lacquers, reaction lacquers, two-componentlacquers, disperse dyestuffs for weather-fast coatings and size colours.The printing colours comprise those for paper, textile and metal sheetprinting. The macromolecular substances can be of natural origin, suchas caoutchouc, or they can be obtained by chemical modification, such asacetyl cellulose, cellulose butyrate or viscose, or they can besynthetically produced, such as polymers, polyaddition products andpolycondensates. Examples are plastic masses such as polyvinyl chloride,polyvinyl acetate, polyvinyl propionate; polyolefines, e.g. polyethyleneor polypropylene; polyesters, e.g. polyethylene terephthalate;polyamides, superpolyamides, polymers and copolymers from acrylicesters, methacrylic esters, acrylonitrile, acrylamide, butadiene,styrene; as Well as polyurethanes and polycarbonates. The substancespigmented with the claimed products may be present in any form.

The compounds used according to the invention have excellent pigmentproperties and are not only eminently fast to wet processing, oil, acid,lime, alkali, solvents, overcoating, overspraying, sublimation andstable to heat and vulcanisation, but they also give very good yields,they can easily be dispersed in plastic materials and have outstandingfastness to light and weather.

The parts given in the examples are parts by weight.

EXAMPLE 1 (a) 8 parts4-(4-chloro-benzoylamino)-l-[4-(3-chlorophenylcarbamoyl)benzoylamino]-anthraquinone which have been finely divided by grindingin a vibrator mill with 2 parts xylene and 160 parts sodium chloride andwashing out the sodium chloride, are ground with a stoving lacquerobtained from 25 parts coconut oil alkyd resin (40% coconut oil), 10parts melamine resin, 50 parts toluene and 7 parts glycol monomethylether in an automatic Hoover- Muller grinding machine. ,The mixture isapplied to the substrate to be coated, the lacquer is cured by stovingat C., and there are obtained violet lacquer coats of good coveringpower and of very good fastness to overcoating and outstanding fastnessto light and weather.

(a-I) Pigmented stoving lacquers of similar fastness properties areobtained by using 15-25 parts of the above alkyd resin or of an alkydresin based on cotton seed oil, dehydrated castor oil, castor oil orsynthetic fatty acids and replacing the above amount of melamine resinwith 10-15 parts of the aforesaid melamine resin or of a condensationproduct obtained from formaldehyde with urea or benzoguanamine.Pigmented stoving lacquers of similar good fastness properties and asimilar shade are obtained by replacing the above4-(4-chloro-benzoylamino)-1-[4- (3chloro-phcnylcarbamoyl)-benzoylamino]-anthraquinone withcorrespondingamounts of finely divided4-(4-chloro-benzoylamino)-l-[4-(4-methyl-phenylcarbamoyl)-benzoylamino]-anthraquinone,

4- (4-chloro-benzoylamino -1- [4-(2,3-dichloro-phenylcarbamoyl)-benzoylamino]-anthraquinone,

4-benzoylamino-1-[4-(2,3-dichloro-phenylcarbamoyl)-benzoylamino-anthraquinone,

4-benzoylamino-1- [4-(2,5-dichloro-phenylcarbamoyl)-benzoylamino]-anthraquinone or 4-benzoylamin0- l- [4-4-nitro-phenylcarbamoyl benzoylamino -anthraquinone.

(a-II) Violet shades also occur by use of the following compounds:

1,4- di- [4-( 2,5 -dichloro-phenyl-carbamoyl-benzoylamino]-anthraquinone,

1,4-di- [4- 2-chloro-S-methyl-phenyl-carbamoyl) benzoylamino]-anthraquinone,

1,4di- [4- (2,4,6-trimethyl-phenyl-carbamoyl)benzoylamino]-anthraquinone,

5, 1,4-di- [4-n-butyl-carbamoyl) -benzoylamino] anthraquinone,

5 -nitrol ,4-di- [4- (n-do decyl-carbamoyl benzoylamino] -anthraquinone,

5-nitro-1,4-di- [4- (2-chloro-phcnyl-carbamoyl)-benzoylamino]-anthraquinone orS-nitro-1,4-di-[4-(4-methyl-phenyl-carbamoyl)- benzoyl] -anthraquinone.

(a-III) The following compounds give blue lacquers,

1,5-dihydroxy-4,8-di- (4-phenyl-carbamoyl-benzoylamino) -anthraquinone,

l,5-dihydroxy-4,8-di- (4-methyl-carbamoylbenzoylamino)-anthraquinone,

1,5-dihydroxy-4,8-di-(n-butyl-carbamoyl-benzoylamino -anthraquinone,

1,8-dihydroxy-4,5-di-(4-phenyl-carbamoyl-benzoylamino)-anthraquinone,

1,8-dihydroxy-4,5-di- 4-methyl carbamoyl-benzoyl anthraquinone,

1,5 -dihydroxy-4,8-di- [4- Z-chloro-phenyl-carbamoylbenzoylamino]-anthraquinone or1,5-dihydroxy-4,8-di-(n-dodecyl-carbamoyl-benzoylamino)-anthraquinone.

(b) If, instead of the amount of pigment stated above, 1 to parts of amixture of titanium dioxide (rutile type) with one of the pigmentsstated in Example 1(a) are incorporated with the lacquer stated inExample 1(a) in a ratio of 0.5-50: 1, then the same method of working upyields lacquer coats of the same fastness properties and a violet orblue shade shifting to white as the content of titanium dioxideincreases.

(c) The 4-(4-chloro benzoylamino)-l-[4-(3-chlorophenyl carbamoyl)benzoylamino anthraquinone described in Example 1(aI) is prepared byheating parts 4-amino-1-(4-chloro-benzoylamino)-anthraquinone with 20parts terephthalic acid dichloride in 400 parts nitrobenzene at 90-110C. until the starting amine can no longer be detected. The4-(4-chloro-benzoylamino)- 1- 4-chloroformyl-benzoylamino -anthraquinonepresent in the form of red needles is isolated and 10 parts thereof areheated in the presence of 3 parts N,N-dimethyl-aniline and 4 parts3-chloro-aniline in 200 parts nitrobenzene at 120145 C. until the acidchloride is completely converted. The product is filtered off withsuction at 100 C., washed with warm nitrobenzene, dimethyl formamide,methanol and hot water, and the dyestuif present in the form of violetneedles is dried at 50 C. in a circulating air cabinet. The samecompound is obtained, when the nitrobenzene is replaced with1,2-dichlorobenzene and the N,N-dimethyl-aniline is replaced withequivalent amounts of sodium carbonate, potassium carbonate or pyridine.

The other compounds stated in Example 1(a)-I) are obtained when the4-amino-1-(4-chloro-benzoylamino)- anthraquiuone is replaced withequivalent amount of 4- amino l-benzoylamino anthraquinone or the3-chloroaniline is replaced with equivalent amounts of 2,3- or2,5-dichloro-aniline or 4-nitro-aniline, or when 1-(4-chloro-benzoyl-amino)-4-(chloroformyl benzoylamino)- anthraquinone isreacted in p-toluidine as solvent and reaction partner at 140-160 C. Theother dyestuffs described in the following examples are obtained in ananalogous manner. 7

The 1,4-di-[4-(2,5-dichloro phenylcarbamoyl) benzoylamino]-anthraquinonedescribed in Example 1(a)- II) is prepared, for example, by introducing20 parts 1,4 diamino anthraquinone at 80 C. with stirring into asolution of 100 parts terephthalic acid dichloride in 250 parts ofaniline-free anhydrous nitrobenzene and stirring at 1051l0 C. until the1,4*diamino-anthraquinone is completely acylated. The mixture is allowedto cool, the precipitated1,4-di-(4-chloroformyl-benzoylamino)-anthraquinone whichis present inthe form of yellowish red prisms is filtered off with suction, theexcess of terephthalic acid dichloride is washed out with anhydrousnitrobenzene, and the nitrobenzene-moist filter cake is reacted, afterdilution with 560 parts of anilinefree anhydrous nitrobenzene, with 39parts 2,5-dichloroaniline in the presence of 20 partsN,N-dimethyl-aniline 10 at 115-120 C., while stirring, until theacylation is complete. The product which is precipitated in the form ofred-violet prisms is filtered off with suction at 100 C., washed withhot nitrobenzene until the discharge liquid is clear, then with alcoholand hot water, and dried at 50 C. in a circulating air cabinet.

The other compounds mentioned in Example 1(a-II) are obtained, when the2,5-dichloro-aniline is replaced with equivalent amounts of4-chloro-3-amino-toluene or 2,4,6-trimethyl-aniline, or the1,4-diamino-anthraquinone is replaced with equivalent amounts of5-nitro-1,4-diamino-anthraquinone and the 2,5-dichloro-aniline withequivalent amounts of p-toluidine, 2-chloro-aniline, nbutylamine at C.or dodecylamine.

The dyestuffs described in the following examples are obtained when thecorresponding acid chlorides and amines are used.

The 1,5-dihydroxy-4,8-di-(4 phenylcarbamoyl)-benzoylamino)anthraquinonedescribed in Example 1(a- III) is prepared for example, by introducing20 parts 4,8-diamino-l,5-dihydroxy-anthraquinone at C. with stirringinto a solution of parts terephthalic acid dichloride in 250 parts ofaniline-free anhydrous nitrobenzene and 20 parts pyridine, and stirringat 80 to C. until the 4,8-diamino-1,5-dihydroxy-anthraquinone iscompletely acylated. The precipitated 1,5-dihydroxy-4,8-di-(4-chloroformyl benzoylamino)-anthraquinone which is present in theform of violet prisms is filtered off with suction, the excess ofterephthalic acid dichloride is washed out with anhydrous nitrobenzene,and the nitrobenzene-moist filter cake is reacted, after dilution with400 parts of anhydrous nitrobenzene, with 60 parts aniline at -160 C.,While stirring, until the acylation is complete. The product obtained inthe form of dark-blue prisms is filtered off with suction at 100 C.,washed with hot nitrobenzene until the discharge liquid is colourless,then with alcohol and hot water, and dried at 50 C. in a circulating aircabinet.

The other compounds mentioned in Example 1(a-III) are obtained when theaniline is replaced with 26 parts 2- chloroaniline or 28 partsdodecylamine in the presence of 12 parts N,N-dimethyl-aniline, or whenthe reaction is carried out, instead of with aniline at 140-16( C., with22 parts n-butylamine at 70 to 80 C., or by introducing methylamine at100 C., or when 4,5-diamino-1,8-dihydroxy-anthraquinone is used asstarting material. The other compounds according to the invention areprepared in an analogous way.

EXAMPLE 2 6 parts of finely divided 4-(3-trifluoromethylbenzoylamino) 1(phenylcarbamoyl-benzoylamino)-anthraquinone are rubbed into 100 partsof a nitrocellulose lacquer consisting of 44 parts collodium wool (oflow viscosity, 35%, butanol-moist), 5 parts dibutyl phthalate, 40 partsethyl acetate, 20 parts toluene, 4 parts n-butanol, and 10 parts glycolmonomethyl ether. After spreading and drying, there are obtained bluishred lacquer coats of outstanding fastness to light and overcoating.

The same results are obtained with the use of nitrolacquers containing10-15 parts of nitro cellulose, 5-10 parts of plasticiser, and 7085parts of a solvent mixture,

' preferably with the use of aliphatic esters such as ethyl 1 1lacquers, possibly in combination with urea, melamine, alkyd or phenolresins.

Lacquer coats of similar fastness properties and a red shade areobtained with the use of corresponding amounts of finely divided insteadof4-(3-trifluoromethylbenzoylamino)-1-(4-phenylcarbamoyl-benzoylamino)-anthraquinone.

Lacquer coats of similar fastness properties and a red shade areobtained with the use of corresponding amounts of finely divided 1,4-di-[4- (butylcarbamoyl) -benzoylamino] -anthraquinone,

1,4-di- [4- (isobutylcarb amoyl) -benzoylamino] -anthr aquinone,

1,4-di- [4- tert.-butylcarbamoyl) -benzoylamino] -anthraquinone,

' 1,4-di- [4- (n-dodecylcarbamoyl) -benzoylamino] -anthraquinone,

1,4-di- [4- (stearylcarbamoyl -benzoylamino] -anthraquinone,

1,4-di- [4- cyclohexylcarbamoyl) -benzoylamin 3 anthraquinone, 1,4-di-[4- fi-phenyl-ethylcarbamoyl -benzoylamino] anthraquinone, 1,4-di- [4-(4-dodecyl-phenylcarbamoyl) -benzoylamino] anthraquinone,

1,4-di- [4- 4-trifluoromethyl-phenylcarbamoyl) -benzoylamino]-anthraquinone,

1 ,4-di- [4- 4-chloro-2-trifluoromethyl-phen ylc arb amoylbenzoylamino]-anthraquinone,

1,4-di- [4- 3-sulphamoyl-phenylcarbamoyl -benzoylamino] -anthraquinoneor 1,4-di-{4- 3 (N-phenylsulphamoyl -phenylcarbamoyl]benzoylamino}-anthraquinone.

Lacquer coats of similar fastness properties and a yellow shade areobtained with the use of corresponding amounts of finely divided1,5-di-[4-(n-butylcarbamoyl) -benzoylamino]-anthraquinone,

1,5-di- [4- (isobutylcarbamoyl -benzoylamino 1 -anth1'aquinone,

1,5-di- [4- (tert.-butylcarbamoyl -benzoylamino] -anthraquinone,

1,5-di- (n-dodecylcarbamoyl -benzoylamino] -anthraquinone,

1,5-di- [4- (stearylcarbamoyl) benzoylamino] -anthraquinone,

1 ,S-di- [4-cyclohexylcarbamoyl) -benzoylamino] -anthraquinone,

1,5 -di- [4-fl-phenyl-ethyl carbamoyl -benzoylamino] anthraquinone,

1,5-di- [4- 4-dodecy1-phenylcarbamoyl -benzoyla mino] anthraquinone,

1,5-di- [4- (4-trifluoromethyl-phenylcarb amoyl -benzoylamino]-anthraquinone,

1,5-di- [4- 4-chloro-2-trifluoromethyl-phenylcarbamoyl) benzoylamino-anthraquinone,

1,5-di- [4- 3-sulphamoyl-phenylcarbamoyl -benzoylamino] -anthraqui noneor 1,5-di-{4- 3- (N-phenylsulphamoyl -phenylcarbamoyl] benzoylamino}-anthraquinone.

EXAMPLE 3 5 parts of finely divided4-benzoylamino-l-[4-(nbutylcarbamoyl) benzoylamino] anthraquinone areground in parts of a paraffin-free drying, unsaturated polyester resinin a porcelain ball mill. 10 parts monostyrene, 5 parts of amelamine/formaldehyde resin and 1 part of a paste of 40 partscyclohexanone peroxide and 60 parts dibutyl phthalate are well stirredwith this material and, finally, 4 parts of a drier solution (10% cobaltnaphthenate in test benzine) and 1 part of a silicone oil solution (1%in xylene) are added. The mixture is applied to primed wood, and thereis obtained a high-gloss Bordeaux lacquer coat which is fast to waterand weather and eminently fast to light.

If the reaction lacquer derived from unsaturated polyester resin isreplaced with amine-curing epoxide resin lacquers, using dipropylenediamine as amine component, then Bordeaux-coloured lacquer-coats ofoutstanding fastness to weather and blooming are obtained. Similarresults are obtained by use of 1,4 di [4 (4methyl-phenylcarbamoyl)-benzoylamino]-anthraquinone and 1,8-di-[4-methyl-phenyl-car-bamoyl -benzoylamino] -anthraquinone.

EXAMPLE 4 (a) 100 parts of a 65% solution of an aliphatic polyester Withabout 8% free hydroxyl groups in glycol monomethyl ether acetate areground with 5 parts of finely divided 4 (4 chlorobenzoylamino) 1 (4methylcarbamoyl) benzoylamino] anthraquinone and then thoroughly mixedwith 44 parts of 67% solution of the reaction product of 1 moltrimethylol-propane with 3 mol toluylene diisocyanate. Withoutadverseetfect on the pot time, application of the mixture and reaction of thecomponents leads to high-gloss red-violet polyurethane lacquer coats ofoutstanding fastness to blooming, light and weather.

Pigmentations of similar fastness are obtained with the use of othertwo-component lacquers derived from aromatic or aliphatic isocyanatesand hydroxyl groupcontaining polyethers or polyesters, as well as withmoisture-drying polyisocyanate lacquers giving polyurea coats.

(b) Pigmentations of similar fastness properties and a similar shade areobtained when corresponding amounts of 4- (4-methoxy-benzoylamino) -1-[4-(n-butyl-carbamoyl benzoylamino] -anthraquinone,

4-(4-chl0ro-benzoylamino)-1- [4-(2,4-dichloro-phenylcarbamoyl-benzoylamino -anthraquinone,

4- 4-chloro-benzoylamino) -1- [4-2-chloro-5-trifluoromethyl-phenylcarbamoyl -b enzoylamino]-anthraquinone,

4- 4-chloro -benzoylamino -1- [4- (4-dode cyl-phenylcarbamoyl)-benzoylamino] -anthraquinone,

4-(3-chloro-benzoylamino -anthraquinone-1-(4-methylcarbamoyl-benzoylamino -anthraquinone or 4- (2-chloro-benzoylamino l- (4-hexadecylcarbamoylbenzoylamino) -anthraquinone areused, instead of the dyestuif mentioned above in Example 4(a).

(c) Pigmentations of similar fastness properties and a similar shade areobtained when corresponding amounts of 1,4-di- [4-2,3-dichloro-phenylcarbamoyl -benzoylaminoanthraquinone,

1,4-di- [4- methylcarbamoyl -benzoylarnino] -anthraquinone,

1,4-di- (4-phenylcarbarnoyl-benzoylamino anthraquinone,

1,4-di- [4- (4-chloro-phenylcarbamoyl -benzoylamino anthraquinone,

1,4-di- [4- 2-chlorophenylcarbamoyl) -benzoylaminolanthraquinone,

1,4-di- [4- 5-nitro-2-methylphenylcarbamoyl -benzoylamino]-anthraquinone,

1,4-di- [4- 4-anilino-phenylcarbamoyl -benzoylamino] anthraquinone,

1,4-di- [4- (4-carbamoyl-phenylcarbamoyl) -benzoylamino]-anthraquinone,or

1,4-di- [4-(pyrenyl-( l )-carbamoyl)-benzoylaminoanthraquinone are used,instead of the dyestutf mentioned above in Example 4(a).

(d) Pigmentations of similar fastness properties and a blue shade areobtained when corresponding amounts of 4-hydroxy-1,4- [4-(2,3-dichloro-phenylcarbamoyl) benzoylamino] -anthraquinone,

1,5 -dihydroxy-4,8-di- (4-methylcarbamoyl-benzoylamino (anthraquinone,

1,5-dihydroxy-4,8-di- (4-phenylcarbamoy1-benzoylamino) anthra quinone,

1,5 -dihydroxy-4,8-di- [4- 4-chloro-phenylcarbamoyl benzoylamino]-anthraquinone,

1,5 -dihydroxy-4,8-di- [4- 5-nitro2-methyl-phenyl-.

carbamoyl -benzoylamino -anthraquinone,

1,5 -dihydroxy-4,8-di- [4- (4-anilino-phenylcarbamoyl) r benzoylamino]anthraquinone,

1,5-dihydroxy-4,8-di- [4- 4-carbamoyhphenylcarbamoyl benzoylamino]-anthraquinone or I 1,5-dihydroxy-4,8-di- [4- (pyrenyl-( 1 )-carbamoylbenzoylamino] -anthraquinone are used, instead of the dyestuff mentionedabove in Example 4(a).

EXAMPLE 5 ,5 parts of a fine paste obtained by kneading 50 parts 4- (4chloro benzoylamino) 1 [4 (4sulphamoylphenylcarbamoyl)-benzoylamino]-anthraquinone with 15 parts ofan aryl polyglycol ether emulsifier and 35 parts of water are mixed withparts of barite as filler, 10 parts of titanium dioxide (rutile type) aswhite pigment, and 40 parts of an aqueous disperse dye containing about50% polyvinyl acetate. The paint is spread and, after drying, there areobtained red coats of very good fastness to lime and cement andoutstanding fastness to weather and light.

The fine paste obtained by kneading is equally suitable for thepigmentation of clear polyvinyl acetate disperse dyes, for disperse dyescontaining copolymers of styrene and maleic acids as binding agents, aswell as for disperse dyes .based on polyvinyl propionate,polymethacrylate or butadiene-styrene.

Coats of similar shade and similar fastness properties areobtained whenthe above 4-(4 chloro-benzoylamino)- 1 [4 (4 sulphamoylphenylcarbamoyl)-benzoylamino]-anthraquinone is replaced withcorresponding amounts of 4- (4-chloro-benzoylamino 1-4-phenylcarbamoylbenzoylamino -anthraquinone,

4- (4-chloro-benzoylamino 1- [4- 2-chloro-phenylcarbamoyl -benzoylamino]-anthraqueinone,

4- 4-ch1oro-benzoylamino 1- [4- 4-chlorophenylcarbamoyl -benzoylamino]-anthraquenone,

4- (4-chlorobenzoylamino 1- [4- (n-butylcarbamoyl) benzoylamino]-anthraquinone,

4- (2-nitro-benzoylamino) -1- [4-(n-butylcarbarnoyl)- benzoylamino]-anthraquinone,

4- 3-nitro benzoylamino )-1-(4-phenylcarbamoylbenzoylamino-anthraquinone,

4-(4-chloro3-nitro-benzoylamino) -1- [4-heptadecyl- (9 -carbamoyl)-benzoylamino] anthraquinone,

4- 3,5-dinitro-benzoylamino 1- (4-stearylcarbamoylbenzoylamino-anthraquinone or 4- (4-chlorobenzoylamino)-1-(4-cyclohexylcarbamoylbenzoylamino -anthraquinone.

Blue coats of similar fastness properties are obtained when the abovedyestuff is replaced with corresponding amounts of 1,5-dihydroxy-4,8-di-[4- (4-sulphamoyl-phenylcarbamoyl -benzoylamino] -anthraquinone,

1,5 -dihydroxy-4,8-di- 4-phenylcarbamoyl-benzoylamino anthraquinone,

1,5dihydroxy-4,8-di- [4- (2-chlorophenylcarbamoyl) benzoylamino]-anthraquinone,

1,5-dihydroxy-4,8-di- [4- (4-chloro-phenylcarbamoy1) benzoylamino]-anthraquinone,

1,5-dihydroxy-4,8-di- [4- (n-butylcarbamoyl) -benzoylamino]-anthraquinone,

1,5 -dihydroxy-4,8-di- [5 n-butylcarbamoyl) -valerylamino]-anthraquinone,

1,5 -dihydroxy-4,8-di- [4- 2-nitro-phenylcarbamoyl benzoylamino]-anthraquinone,

1,5dihydroxy-4,8-di- [4- 3-nitro-phenylcarbamoyl)benzoylamino]-anthraquinone,

1,5-dihydroxy-4,8-di- [4- (4-nitro-phenylcarbamoyl benzoylamino]-anthraquinone or 1,5-dihydroxy-4, S-di- [4-3,4-dichloro-phenylcarbamoyl benzoylamino] -anthraquinone.

EXAMPLE 6 10 parts of a pigment paste mentioned in Example 5 are mixedwith a mixture of 5 parts of chalk and 5 parts of 20% size solution. Ared wall paper coating colour is obtained yielding coats of outstandingfastness to light.

For the preparation of the pigment paste there may also be used othernon-ionic emulsifiers, such as the reaction products of nonylphenol withethylene oxide, or ionic Wetting agents, such as the sodium salts ofalkylaryl-sulphonic acids, for example of dinaphthyl-methane-disulphonicacid, sodium salts of substituted sulphofatty acid esters, and sodiumsalts of paraffin-sulphonic acids in combination with alkyl polyglycolethers.

EXAMPLE 7 A mixture of 65 parts polyvinyl chloride, 35 parts diisooctylphthalate, 2 parts dibutyl tin mercaptide, 0.5 part titanium dioxide,and 0.5 part 4-(4-chloro-benzoyl- 4- (4-chloro-benzoylamino 1- [4- 2,5-dichloro-phenylcarbamoyl -benzoylamino] -anthraquinone,

4- (4-chloro-b enzoylamino -1- [4- (4-trifluoromethylphenylcarbamoyl)-benzoyl amino] -anthr aquinone,

4- (4-chloro-benzoylamino) 1-[4- (4-methoxy-phenylcarbamoyl)-benzoylamino] -anthraquinone,

4- (4-chloro-benzoylamino 1-[4- 3-sulphacyclopentyl-S,S-dioxide-carbamoyl)-benzoy1amino]-anthraquinone,

4- (3-trifluoromethyl-benzoylamino -1- (4-butylcarbamoyl-benzoylamino-anthraquinone or 4- (4-nitro-b enzoylamino l-(4-phenylcarbamoyl-benzoylamino) -anthraquin'one.

Colourations of a similar shade and similar fastness properties areobtained when the above dyestuif is replaced with corresponding amountsof 1,4-di- [4- (n-butyl-carbamoyl) -benzoylamino] -anthraquinone,. Y

1 ,4-di- [4- (isobutylcarbamoyl -benzoylamino] -anthraquinone,

1,4-di- [4- (n-dodecylcarbamoyl) -benzoylamino] -anthraquinone,

1,4-di- [4- (4-chloro-phenylcarbamoyl) -benzoylamino] anthraquinone,

1,4-di- [4- (4-carbamoylphenylcarbamoyl) -benzoylamino] -anthraquinone,

1,4-di- [4- 4-sulphamoyl-phenylcarbamoyl) -benzoylamino] -anthraquinone,

1,4-di- [4- 3-hydroxy-propyl-carbamoyl) -benzoylamino] -anthraquinone, I

1,4-di- [4- (4-acetylphenylcarbamoyl) -benzoylamino] anthraquinone.

Colourations of a yellow shade and similar fastness properties areobtained when the above dyestufi is replacedwith 4-hydroxy- 1 ,S-di- [4-(butylcarbamoyl) -benzoylamino] anthraquinone,

1,5 di- 4-phenylcarbamoyl-benzoylamino anthraquinone,

1,5 -di- [4- (methtylcarbamoyl) -b enzoylamino] -anthraquinone,

1,5 -di- 3-phenylcarbamyl) -benzoylamine-anthraquinone,

1,5-di- 3- (4-chloro-phenylcarbamoyl) -benzoylamino] anthraquinone,

1 ,8-di- [4- (methylcarbamoyl) -benzoylamino] -anthraquinone,

1,8-d i- (4-phenylcarb amoyl-b enzoylamino -anthraquinone, k v

1 ,8-di- [4- 4-sulphamoyl-phenylcarbamoyl) -benzoylamino]-anthraquiuone,

1,8-di- [4- (4-carbamoyl-phenylcarbamoyl) -benzoylamino] -anthraquinoneor 1,5-di-[4- (4-carbamoyl-phenylcarbamoyl) benzoylamino]-anthraquinone.

EXAMPLE 8 0.2 part of finely divided 4-(4-chlorobenzoylamino)-l-(fl-phenylcarbamoyl benzoylamino)-anthraquinone is mixed with 100parts of a polyethylene, polypropylene or polystyrene granulate. Themixture can either be immediately injection-moulded at 220 to 280 C. inan injection moulding machine, or it can be worked up in an extruder toproduce coloured rods, or on mixing rolls to produce coloured roughsheets. If desired,-the rodsor rough sheets are granulated andinjection-moulded in an injection-moulding machine.

The red mouldings are very fast to light and migration. In a similarmanner, synthetic polyamides of caprolactam or adipic acid andhexamethylene diamine or condensation products of terephthalic acid andethylene glycol can be coloured at 280-300" C., possibly under anitrogen atmosphere. Similar red moldings are obtained by use ofl,4-di-[4-(n-butyl-carbamoyl) benzoylamino1- anthraquinone, andsimilarly blue moldings are obtained by use ofl,5-dihydroxy-4,8-di-(methylcarbarnoyl-benzoylamino -anthraquinone.

EXAMPLE 9 1 part of finely divided4-benzoylamino-l-(4-phenylcar-bamoyl)-benzoylamino-anthraquinone, 10parts titanium dioxide (rutile type) and parts of a copolymer derivedfrom acrylonitrile-butadiene-styrene and present in powdered form aremixed and coloured on mixing rolls at -180 C. A wine-red rough sheet isobtained, which is granulated and injection-moulded at 200-25.0 C. in aninjection-moulding machine. There are obtained wine-red mouldings ofvery good fastness to light and migration and excellent thermalstability.

In a similar manner, but at temperatures of 180-220" C. and without theaddition of titanium dioxide, synthetic materials based on celluloseacetate, cellulose butyrate and mixtures thereof are coloured withsimilar fastness properties. Similar wine-red moldings are obtained byuse of 1,4-di- [4-(4-methyl-phenyl-carbamoyl)-benzoylamiuo]-anthraquinone and similar orange-colored moldings areobtained by use of 1,5-di-[4-(4-methyl-phenyl-carbamoyl-benzoylamino]-anthraquinone.

EXAMPLE 10,

yl-carbamoyl benzoylamino) anthraquinone and blue transparent granulatesare obtained with 1,5-dihydroxy- 4,8 -di (4 phenyl-carbamoyl)benzoylamino-anthra qumone.

EXAMPLE 11 90 parts of a slightly branched polypropylene glycol with amolecular Weight of 2500 and a hydroxyl number of 56, 0.25 partendoethylene-piperazine, 0.3 part tin (II) octoate, 1.0 part of apolyether siloxane, 3.5 parts of water, 12.0 parts of a dispersion of 10parts of finelydivided 4-benzoylamino-l-(4-methylcarbamoyl)benzoylamino1- anthraquinone in 50 parts of the stated polypropyleneglycol are well mixed with one another and subsequently intimately mixedwith 45 parts toluylene diisocyanate (80%, 2,4- and 2,6-isomer), andpoured intoa mould. The mixture becomes turbid and formation of foamtakes place. After 70 seconds, an intensely wine-red soft poly urethanefoam has formed the pigmentation of whichvhas outstanding fastness tolight. 7

Reddish blue polyurethane soft foams of a similar lightfast pigmentationare obtained when the 4-benzoylamino- 1-4-methylcarbarnoyl-benzoylamino)anthraquinone is replaced with corresponding amounts of2-bromo-4-(4-methy1-anilino)-1-(4-pheny1carbamoylamino) -anthraquinone,I 2-bromo-4-(4-methyl-2,6-diethyl-anilino)-1 (4-phenyl- EXAMPLE 13 r Aprinting ink prepared by grinding 35 parts of finely divided 4benzoylamino 1 (4 phenylcarbamoylbenzoylamino)-anthraquinone and 65parts linseed oil and adding 1 part" of a desiccator (Co-naphthenate,50% in' test benzine) yields red ofiset prints of high brilliancy andstrength of colour and very good fastness to light and lacquering. Theuse of this printing ink in book printing, haliographic printing,lithographic printing or steel engraving printing leads to red prints ofsimilar fastness properties. If the pigment is used for colouring pastesfor sheet metal printing, or low viscosity pastes for; heliogravure andprinting inks, red prints of similar fastness properties are obtained.

.Ifi the 4 benzoylamino 1 (4 phenylcarbamoylbenzoylamino) anthraquinoneis replaced with corresponding amount of 4- 3-chloro-benzoylamino) 1'(2,5 -dichloro-4-pheny1- wcarbamoylbenzoylamino)-anthraquinone,

4-benzoylamino-1-(4-hydroxy-3-phenylcarbamoylbenzoylamino)-anthraquinone, 1

4-(4-chloro-benzoy1amino 1- 6-phenylcarbamoy1- naphthoyl- (2 -amino-anthraquinone,

4- (4-chloro-b enzoylamino 1- [4-(4-phenylcarbamoylphenyl)-benzoylamino]-anthraquinone,

4-benzoylamino-1-[4-(4-phenylcarbamoyl-phenoxy)-benzoylamino]-anthraquinone,

4-benzoylamino-1-{4-(2-phenylcarbamoyl-benzoyl)-benzoylamino]-anthraquinone,

4-benzoylamin0-1- [4-(4-phenylcarbamoyl-phenylsulphonyl)-benzoylamino]-anthraquinone,

4-(4-nitro-benzoylamino)-1-(5-phenylcarbarnoylvalerylamino)-anthraquinone,

then prints of a similar shade and similar brilliancy and fastness areobtained.

If the above pigment is replaced with corresponding amounts of 1 ,4-di-[4- (n-dodecylcarbamoyl) -benzoylamino] anthraquinone,

2-phenoxy- 1,4-di- [4-4-trifluoromethyl-phenylcarbamoyl)-benzoylamino]-anthraquinone,

1,4-di-[5-(n-butylcarbamoyl)-valerylarnino]- anthraquinone,

1,4-di-[4-(n-butylcarbamoyl)-benzoylamino]- anthraquinone,

1,4-di-[2,5-di-chloro-4-(n-dodecylcarbamoyl)benzoylamino]-anthraquinone, V

1,4-di-[4-hydroxy-3-(n-dodecylcarbamoyl)-benzoylamino]-anthraquinone,

1,4-di- [6- n-dodecylcarbamoyl) -naphthoyl- (2 amino]-anthraquinone,

1 ,4-di- [4- [4- (n-dodecyl-carbamoyl) -phenyl]benzoylamino]-anthraquinone,

1 ,4-di- [4- [4- n-dodecyl-carb amoyl) -phenoxy]-benzoylaminoJ-anthraquinone,

1,4-di- [4- [2-(n-dodecylcarbamoyl benzoyl] -benzoylamino]-anthraquinoneor 1,4-di- [4- [4- (n-dodecylcarbamoyl -phenylsulphonyl]benzoylamino]-anthraquinone,

then prints of a similar shade and similar brilliancy and fastness areobtained.

If the above pigment is replaced with corresponding amounts of I i 1,5-dihydroxy-4, 8-di- (4-phenylcar-b amoyl-benzoylamino -anthraquinone,

1,5 -dihydroxy-4, 8-di-' 4-methylcarbamoyl-benzoylamino)-anthraq-uinone,

1, 5 -dihydroxy-4, 8-di- [4- n-butylcarb amoyl-benzoylamino]-anthraquinone, v

1,5-dihydroxy-4,8-di- [5- (n-butylcarbamoyl) valerylamino]-anthraquinone,

1,5-dihydroxy-4,8-di- [2,5 -dichloro-4- n-dodecylcarbamoyl)-benzoylamino -anthraquinone,

1 ,5 -dihydroxy-4, 8-di- (4-hydroxy-3-phenylcarbarnoylbenzoylamino-anthraquinone,

1,5-dihydroxy-4, 8-di- (6-phenylcarbamoyl-naphthoyl- (2 -arnino-anthraquinone,

l,5-dihydroxy-4,8-di- [4- (4-phenylcarb amoyl-phenyl) benzoylamino]-anthraquinone,

1,5-dihydroxy-4,8-di- [4- 4-phenylcarbamoyl-phenoxy) benzoylamino]-anthraquinone,

1 ,5 -dihydroxy-4, 8-di- [4- (2-phenylcarbamoyl-benzoyl) ben zoylamino]-anthraquinone or 1,5 -dihydroxy-4, 8-di- [4- 4-phenylcarbamoyl-phenyl-1 sulphonyl) -benzoylamino] -anthraquinone,

then prints of a blue shade and similar fastness are obtained.

EXAMPLE 14 A printing paste is.prepared from 10 parts of a pigment finepaste described in Example 5, parts of 3% tragacanth, 100 parts of a 50%eg albumin solution and 25 parts of a non-ionic wetting agent. A fabricof textile fibres is printed, steamed atvl00 C., and a red or blue printis obtained, which is characterised by excellent fastness properties,especially fastness to light. Instead of tragacanth and egg albumin,other binding agents suitable for fixation on the fibre, for example,those derived from synthetic resin, British gum or cellulose glycollate,can be used in the printing mixture. I

EXAMPLE 15 A mixture of 100 parts of light crepe, 2.6'parts sulphur, 1part stearic acid, 1 part mercapto-benzothiazole, 0.2 parthexamethylene-tetramine, 5 parts zinc oxide, 60 parts chalk and 2 partstitanium dioxide (anatase type) is coloured on mixing rolls at 50 C.with 2 parts 4-benzoy1- amino-l-[4 (n-butylcarbamoyl) benzoylamino]anthraquinone and then vulcanized at C. for 12 minutes. A wine-redvulcanisation product of very good fastness to" light is obtained.

A wine-red product is'obtained also by use of 1,4di- [4-(3,5-dichloro-phenyl-carbamoyl)-benzoylamino] anthra quinone and ayellow product is obtained with 1,8-di[4- (3,S-dichlorophenyl-carbamoyl)benzoylamino] anthraquinone.

EXAMPLE 16 100 parts of a 20% aqueous paste of 4-(3trifluoromethyl-benzoylamino -1- [4- (4-nitro phenylcarbamoyl)benzoylamino]-anthraquinone, prepared, for example, by dissolving thedyestuif in 96% sulphuric acid, pouring the solution on to ice,filtering and washing with 'water until neutral, are admixed in astirrer with 22,500 parts of an aqueous, approximately 9% viscosesolution. The colored nitrile in dimethyl formamide, which has beencolored with finely divided 4-(4-chloro-benzoylamino)-1-[4-chlorophenyl-carbamoyl] -benzoylamino] -anthraquinone,

1,4-di- [4- (4-sulfamoyl-phenyl-carb amoyl) -benzoylamino]-anthraquinoneor 4-hydroxy- 1 ,5-di- [4- (4-sulfamoyl-phenyl-carb amoyl) benzoylamino]-anthraquinone,

is subjected to a dry spinning process.

EXAMPLE 17 10,000 parts of paper pulp containing 4 parts cellulose per100 parts are treated in a hollander for about 2 hours. During thistime, there are added at intervals of 15 minutes 4 parts of rosin size,then 30 parts of an approximately 15% pigment dispersion obtained bygrinding 4.8 parts4-(3-trifluoromethyl-benzoylamino)-1-[4-(4-chlorophenyl-carbamoyl)-benzoylamino]-anthraquinone with 4.8 partsdinaphthyl-methane-disulphonic acid and 22 parts of water in a ballmill, and then parts aluminium sulphate. After finishing in a papermachine, a bluish red paper of outstanding fastness to light isobtained. Similar results are obtained with1,4-di-[4-(n-butyl-carbamoyl)- benzoylamino]-anthraquinone andl,5-dihydroxy-4,8-di- (4-methyl-carbamoyl-benzoylamino -anthraquinone.

EXAMPLE 18 The blue and red pigmented papers produced according toExample 17 are impregnated with a 55% solution of an ureaformaldehyderesin in n-butanol and stoved at 140 C. A bluish red laminate paper ofvery good fastness to migration and outstanding fastness to light isobtained.

A laminate paper of similar fastness properties is obtained bylaminating a paper which was printed by the helio-gravure process with aprinting paste containing the red pigment fine pastes described inExample 5 and Watersoluble or hydrolysable binding agents.

EXAMPLES 19-212 Fast pigmented stoving lacquers of the shades stated inthe following table are obtained according to Example 1(a), but usingcorresponding amounts of the finely divided dyestufis stated in thetable, instead of 4(4-chlorobenzoylamino)-1-[4(4-chloro-phenylcarbamoyl)benzolyamino1-anthraquinone:

Shade Ex. Dyestufi v 19 4-(4-chloro-benzoylamino)-1-[4-(n-butylcarbam-Red.

' oyl)-benzoy1amin01-anthraquinone. 20 4-(4 chloro-benzoylamino)-l-4-(4-chloropheny1- Bluish red.

carbamoyl)-benzoy1amino -anthraquinone. 21 4-(4-chloro-benzoylamino)-1-4(4-carbamoyl- Red. pllliienylcarbamoyb-benzoy amino]-anthraq none. 22-4-(4-chloro-benzoylamino)-1-(4-phenylcarbarn- Red.

oylbenzoylamino)-anthraouinone. 23 4-(4-chloro-benzoylamino)-1-4-(2-chlorophenyl- Bluish red.

carbamoyD-benzoylamino -anthraquinone. 24 4-(4-chloro-benzoylamin0)-14-(3-diehloro- Red.

p11enylcarbamoyl)-benzoyaminol-anthraqmnone. 254-(4'chlorobenz0y1arnino)-l-[4-(2-nitrophenyl- Red-brown.carbamoyl)-benzoylamino1-anthraquinone. 26 4-(4-ehloro-benzoylamino)-1-4-(3-nitrophenyl Bluish red.

carbamoyD-benzoylamino -anthraquinone. 27 4-(4-ch1orobenz0ylamino)-1-4-(4-nitrophenyl- Red. earbarnoyl)-benzoylarnino -anthraquinone. 284-(4-chloro-benzoylamino)-1- 4-(4-trifluoro- Bluish red.

' methyl-phenylearbamoyl)-benzoy1amino]- anthraquinone. 294-(4-chloro-benzoylamino)-1-[4-(3-sulphamoyl- Red.

phenylcarbamoyl)-benzoylamino]-anthraqu1- none. 304(4-ehloro-benzoylamino)-1-(S-thla-eyclopentyl- Red.

S,S-dioxide-carbamoyl)-benzoy1amino]- anthraquinone. 314-benzoylamin0-1-[4-(2-chloro-phenylcarbamoy1- Yellewlshbenzoylamino]-anthraquinone. red. 32-4-benzoylamino-1-[4-(B-chlorephenylcarbam- Red.

. oyl)-benzoylamino1-anthraquinone. 334-benzoylamino-1-[4-(2,5-dichl0ro-phenylcar- Red.

bamoyD-benzoylaminol-anthraquinone. 344-benzoylamino-1-[4-(4-nitro-phenylcarbamoyD- Red.

benzoylamino]-anthraquinone.

Shade 354-(4-methoxy-benzoylamino)1-[4-(2,5-rliehlorophenylcarbamoyl)-benzoylamino]-anthraquinone.

364-(4-methoxy-benzoylan1ino)-1-[4-(4-nitrophenylcarbarnoyl)-benzoylamino]-anthraquinone.

37 4-(3-trifluoromethyl-benzoylarnino)-1-(4-phenylcarbamoyl-benzoylamino)-anthraquinone.

38 4-(.t-trifluoromethyl-benzoylamino)-1-[4-(4-ehloro-phenylcarbamoyl)-benzoylamino] anthraquinone.

39 4-(4-n1trobenzoylamino)-l-(4methylcarbamoylbenzoylamino)-anthraquinone.

40 4-(4-nitro-benzoylamino)-1-[4-(n-butylcarbam- 0yl)-benzoylamino]-anthraquinone.

414-(4-mtro-benzoylamino)-[4-(n-dodecylcarbamoyl)-benz0ylamin01-anthraquinone.

424-(-nitro-benzoylamino)-1-[4-(2-chloropl1enylcarbamoyl)-benzoylamino1-authraquinone.

4-(4-nitro-benzoylamino)-1-[4-(4chlorophenylcarbamoyl)-benzoylamino]-anthraquinone.

444-(4-nitro-benzoylamino)-1-[4-(2,5-dich1orophenylcarbamoyl)-benzoylamino]-anthraqumone.

454-(2,4-dich1orobenzoy1amino)-1-[4-(5-carb0xypentylcarbamoyl)-benzoylamino]-antl1raquinone.

464-(2,4-dichloro-benzoylamino)-1-{4-[2-hydroxyethylamlno)-ethylcarbamoyl]-benzoylamino)-anthraqumone.

474-(2,4-dichloro-benzoylan1ino)-1-[4-(3-butoxyprqpylcarbamoyl)-benzoylamino]-anthraqumone.

484-(2,4-dichloro-benzoylamino)-1-[4-(3,5dichlorophenylearbamoyl)-benzoylamino1-anthraquinqne.

494-(2,5-d1chloro-benzoylamino)-1-[4-(2-ethylmereaptoethylcarbamoyl)-benzoylamino]-anthraquinone.

504-(2,S-diehloro-benzoylamino)-1-[4-(benzoylmethylcarbamoyl)-benzoylamino]-antl1raquinone.

514(2,5-diohl0r0-benzoylammo)-1-[4-(2,3,5-trichloro-phenylcarbamoyl)-benzoylamino]-anthraquinone.

52 4-(4methyl-benzoylamino)-1-[4-(5-chl0ro-2-nitro-phenylcarbamoyl)-benzoylamino]- anthraquinone.

534-(4-methyl-benzoylamino)-1-[4-(2,4-dinitrophenyloarbamoyl)-benzoylamino]-anthraquinone.

54 4-(4-methyl-benzoylamino)-1-[4(6-bromo2,4-dinitro-phenylearbamoyl)-benzoylamino1- anthraquinone.

554-(4-methyl-benzoylamino)-1-[4-(4-methylphenylcarbamoyl)-benzoylamino]-anthraquinone.

56 4-aeetylamino-1-[4-(4-methyl-phenylcarbamoyl)-benzoylamino]-anthraquin0ne.

57 5-nitro-4benzoy1amino-1-[4-(4-methyl-phenylearbamoyl)-benzoylamino1-anthraquinone.

58 2-bromo-1-[4-(4-methyl-phenylcarbamoyl)-benzoylaminoM-(4-methyl-benzenesulphamido)-anthraquinone.

59 4-(4-trifiuoromethyl-benzoylamino)-1-[4 (4-methyl-phenylcarbamoyl)-benzoylamino]- anthraquinone.

60 4'1)enzoylamino-1-[4-(5-ohl0ro2-trifluoromethyl-phenylearbamoyl)'benzoylaminok anthraquinone.

614-benzoylamino-1-[4-(5-nitro-2-methyl-phenylcarbamoyl)benzoylamino]-anthraquinone.

624-benzoylamino-1[4-(2-ehloro-5methyl-phenylearbarnoyl)-benzoylaminoI-anthraquinone.

63. 4-benz0y1amino-1-[4-(3,5-bis-trifluoromethy1-phenylearbamoyl)-benzoylamino]-anthraquinone.

644-benzoylamino-1-[4-(2,4,6-trimethyl-phenylcarbamoyl)-benzoylamino1-anthraquinone.

65 4-(3'chloro-benzoylamlno)-1-[4-methyl-3,6-

diethyl-phenylcarbamoyl)-benzoylam.ino]- anthraquinone.

664-(3-ehloro-benzoy1am1no)-1-[4-(5,6,7,8tetrahydro-naphthyl-(l)-earbamoyl)-benzoylamino]-anthraquinone.

674-(3-eh1oro-benzoylamino)-1-[4-cyc1ohexylphenycarbamoyl)-benzoylamino]-anthraqumone.

68 4-(3-chloro-benzoylamino)-1-(naphthyl-(1)-earbamoyl-benzoylamino)anthraquinone.

69 4-(4-chloro-benzoylamino)-1-(4-anthracenyl-(2)-carbamoyl-benzoylamino)-anthraquinone.

70 4-(4ehloro-benzoylamino)-l-(4-pyrenyl-(1)-carbamoyl-benzoylamino)-anthraqu1none.

714-(4-chloro-benzoylam1no)-l-[4-(4-anilino-phenylcarbamoyl)-benzoylamino]-anthraquinone.

724-(4ch1om-benzoylamino)-1-[4-(4-phenoxyphenylcarbamoyl)-benzoylamino]-anthraquinone.

73-4-(4-nitro-benzoylamino4-(4-[4-(4-methylaniline)phenylearbamoyl]-benzoy1amino)-anthraqulnone.

744-(4-nitro-benzoylamino)-1-{4-(4methoxyaniline)-phenylcarbamoyl]-benzoylaminolanthraquinone.

754-(4-nitro-benzoylamino)-1-[4-(4-methylsulphonyl-phenylearbamoyl)-benzoylamlno]anthraquinone.

Bluish red.

Violet.

Bluish red.

Red.

Yellowish red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Red.

Ex- Examample Dyestufl Shade ple Dyestufi Shade 356 1,4-dil4-(d-niethzll-phenylcarbamoyl)-ben- Bluish red.132552,;{,fififigfigfigfiiffi Blue zoy ammo -an raqumone. 3 3571,4-di-(4-phenylcarbamoyl-benzoylamino)-an- Red. 5 "i,ggggfifig'gqgfigfigffi gfifigi Do thmqmnone-ifcarbowhc acid ethyl ester- 394.1,5-dihydroxy-4,8-di-l4-(2,4-dicyano-phenylcarbamoyl)- Do. 358 1,4-dl-[4-(4-chloro-phenylearbamoyl)-benzoyl- Red. b z 1au i a thra ui o g g l-g g q y and a95 1,5-dlihgdrox3i-43fidi-lflZ-ghloro-fa-ghydrfxyethyl-Do. o a o n a no 359 1,%di-(4-g4$111131}amggI-phenylcarbamoyl)- Yellow.iiitiuggini n my car m y] 8 my m1 3! a no Taqmnone- 396..."1,5-dihydroxy-4,8-di-[4-(ti-carbamoylnaphthyl-(2)- D0. 3601,8-dl-(2,3,5,6-tetrachloro-4-n1ethylcarbamoyl- Do. 10 carbamoyl)bemoy1amino] anthmquinone beazoylaminomnthraqmnones97"---1,5-dihydroxy-4,8-di-[4 (2-carbamoyl4-sulphamoyl- Do. 351 'P ypheuylcarbamoyl)-benzoylamino1-anthraqulnone.

beuzoylammw-anthraqwnone- 398-1,5-dihydroxy-4,8-di-[4-(4-phenylazophenylcarbamoyl)- Do. 3621,8-d1-[4-(2-nitr04-carbamoyl phenylcar- D0. benzoylamino]anthraquinone.

banwy p qy laqmnone. 3991,5-dihydroxy-4,8-di-(4pyridy1-(2)-carbamoyl-benzoyl- D0. 3631,5-d1hydroxy-4,8-d.\-(4-1nethylcarbamoylben- Blue. amino)-anthyaquinoneZ0Y1a111in0)-Hnthmq\11nne- 400"-.-l,5-dihydroxy-4,8-di-[4-('y-picolylcarbamoyl)-benzoyl- D0. 3641,5-dihydIoxy-4,8- -bu y fl bfl y aminol-anthraquinone.

y q 401 1,5-dihydroxy-4,8-di-[4(2-phenyl-benzotriazoly1-(5)- Do. 365 yyp y phe y D0. earbamoyl)-benzoylamino]-anthraquinone.

y qy aminol-amhraqmnone. 402---1,5-dihydroxy-4,8-di-(4-thiaz0lyl-(2)-carbamoy1- Do. 3661,5-dihydroxy-4,8-d1-[4-(2,4-d1carbamoylphenyl- DO.benzoylamino)-anthraquinone.

a ba y )be y a l-a aqu 4031,5-dihydroxy-4,8-di-[4-(fi-methoxy-benzothiazolyl-(Z)- Do. 3671,5-dihydroxy-4,8-di-(4-phenylcarbamoylben- D0.earbamoyl)-benzoylamino]-anthraquinone.

zoylarnino)-anthraquinone. 4041,5-dihydroxy-4,8-di-[4-(Z-methyl-benzothiazolyl-(6)- Do.

carbamoyl)-benzoylaminol-anthraquinone.

EXAMPLES 368491 What is claimed is: When a pigmented paper is producedaccording to Dyesmfi of the formula: Example 17 with the use of thedyestuifs stated in the I 0 table, or when paper is printed with aprinting paste conl taining a fine paste prepared according to Example 5with the use of the dyestuffs stated below as well as watersoluble orhydrolysable binding agents, and when the paper thus pigmented orprinted is treated according to I Example 18, then fast laminated papersof the specified shades are obtained.

II 0 Hill-R Example Dyestufl Shade 368...-..4-(4-chloro-benzoylamln0)-1-(4-methylcarbam- Red-violet.

oyl-benzoylamino)-anthraquinone. 3694-(4-ch1oro-benzoylamino)-1-[4-(4-nitrophenyl- Red.

carbamoyl)-benzoylamin0]-anthraquin0ne. 370..--..4-benzoylamino-l-[4-(n-bntyl-carbamoyl)- Bordeaux.

benzoylaminol-anthraquinone. 371--....4-benzoylamino-1-(4-phenylcarbamoylbenzoyl- Red. 01

amino)anthraquinone. 372 4-benzoylamino-1-[4-(2-chloro-phenylcarbamoyn-Red. III 0 HN-R benzoylamlnolanthraquinone. I I 373-.--..4-benzoy1amino-l-[4-(4-nitro-phenylcarbamoyl)- Red.

benzoylamlno]-anthraquinone. 374-.....4-(3-trifiuoromethyl-benzoylamino)-1-(4-butyl- Red.

earbamoyl-benzoy1amino)-anthraquinone. 3754-(4nitro-benzoy1amin0)-l-[4-(4-chloropl1eny1- Red.

carbamoyl)-benzoy1amino1-anthraquinone. 375".-.2-bromo-1-[4-(4-eh1oro-phenylcarbamoyl)- Red. I 4

benzoylamino1+(4-methyl-benzenesu1ph- R-NH l amido)-anthraquinone. 377.-1,4-di-[4-(2,3-dichloro-phenylcarbamoyl)- Bluish red. Whl'filfl R 18benzoylaminol-anthraquinone. 37s"-.. 1,4-di-[4-(2,5-dichlorophenylcarbamoyl)- Violet.

benzoy1amino1-anthraquinone. C O-NH 3791,4-di-[4'(2ch1oro-E-trifluoromethyl-phenyl- Bluish red. so.

carbamoyl) -benzoylam.ino]-anthraquinone. C 0 380.1,4-dj[4-(3-sulphamoyl-phenylcarbamoyl)- Red.

benzoylamino]-anthraquinone. 381..1,4-di-[4-(4-carbamoyl-phenylcarbamoyl)- Bluish red. and Y denotesbenzoylamino1-anthraquinone. 5 5 3825,8-dich1oro-1,4-di-[4-(n-butylcarbamoyD- Red. 01

benzoylaminol-anthraquinone. 383....-.1,5-(4-phenylcarbamoy1-benzoylamino)- Yellow. 00

anthraquinone. 384- 1,51;di-[4 (it-sulphlam%%1-pheny1carbamoyl)- Do.

enzoy amino -an raqulnone. 385m 1,5 [M 4 carbamoyl phenylcarbamoyl) Thedyestuff of claim 1 belng. 4 (4chloro benzoyl 8 bgnz[o3zl2am iol]lianthrgqmi on% I) D 0 amino) 1 [4 (3 sulpha cyclopentyl S,S dioxide-3 6"..- 15- i-4- 5- c oro-p eny car amoy 0.

-bemoylminol anthmquinone carbamoyl) benzoylammo] anthraqulnone. 387.,1,5-dill)1ydro1i'-g,8-di-[i1-(ls-dichlggophenyl- Blue.

car amoy enzoy ammq-an raqumone. 388..."1,5-diydroig-,8-di-[%-(4-;nefhog-phenyl- Do. References Clted ear amoyenzoy 81111110 -an raqmnone. 389 1,5-dihydroxy-4,8-di-[4-(4methy1-phenyl- D0. UNITED STATES PATENTS 390 grg gpgg g a y g gg g ug ge- Do 3,361,765 1/ 1968 Weber et al. 260-329.2

----- y -me 0 yeny (4-butylcarbamoyl-benzoylamino)- I 2,123,375 7/1938Ml g 260-60 391 1 iii fi ii'i il-h dr h D4 8 (11 D 1 y oxyy oxy-p eny o.

, (4%?enylparbamoyhbmoylammo) HENRY R. JILES, Primary Examiner an raumone.

q C. M. SHURKO, Assistant Examiner EXAMPLES 392-404 CL Printing pastesprepared according to Example 13, but 260-2949, 295 T, 303, 308, 316,327 R, 327 TH, 346.2 using corresponding amounts of the dyestuifs statedin R, 347.2, 347.3, 370, 371, 372, 373, 374, 375, 376, 377, the table,yield fast offset prints in the specified shades. 378, 379, 380, 381

- UNITED STATES TENT OFFI E CERII FICA TE U I CORRECTI ON Patent No.3,699 l26 Dated October 17 1972 Karl-Heinz Peters et al Inventor(s) I II It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 3, line 42 "a'lky" should read alkyl--.

Column 6, line 29, "hereto" should read hetero-:. Column 10, line 66,"vylene" should read xylene--.

Column 13 line 68, "anthraqueinone" should read anthraquinone-l-.

Column 13, line 70, "anthraquenone" should read anthraquinone--.

Column 14, line 12, "aminol] should read amincj Column 15, line 55,"(methtyl carbamoyl)-" should read (methylcarbamoyl) I Column 15, line57, "phenylcarbamyl) should read ""P nylc'arbamoyl) V I Column 15, line57, "-benzoylamine-" should read benzoylamino- Column 17 line 51,-"antraquinone should read anthraquinone Column 17 line 48, "3meethylcarbamoyl-" should read 3-methylcarbamoyl- Column 2l, Ex. 21, "Red"should read Bluish red Column 21 Ex. 24, "Red" should read Bluish redFoam po-xoso I0-69) I LJSCOMM'DC 60376-P69 Q U.SI GOVERNMENT PRINTINGOFFICE: I969 0-365-33 UNITED STATES PATENT OFFICE CERTIFICATE U FCORRECTION Page 2 Patent No. 3,699,126 Dated October 17 1972 Karl-HeinzPeters et al 1 I nventor(s) It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column '26 BX. 223, "Dol should read Do.--.

Column 26, Ex. 236, "anthraquim'oneY should read anthraquinone Column26, Ex.) 270 "banzoy'lemino)-" should read benzoylamino) Column 27, BX;309, "anthraquinne" should read Yanthraquinone Column 28., Ex. 318,anthrq-" should read -anthr a Column 28, 319, "-benxoylamino) shouldread benzoylam-ino) Column 28, Ex. 323, "-carbanamide." should readcarbonamide.

Column 28, BX. 329, "-banzoyl" should read benzoyl Column 28, Ex. 342,"btuyl-" should read -butyl- Column 30, Ex. 39s, "di4(4" should readdi-(4- Signed and sealed this 11th day of March 1975.

(SEAL) Attest: v

RUTH c MASON. c. MARSHALL DANN Attesting Officer Commissioner of Patentsand Trademarks FORM PO'WSO (10459) I v I I uscoMM-oc scan-ps9 U.S.GOVERNMENT PRINTING OFFICE: 1969 0-366-334

